Electrokinetics in porous media entails complex transport processes occurring upon the establishment of electric potential gradients, with a wide spectrum of environmental applications ranging from remediation of contaminated sites to biotechnology. The resulting electric forces cause the movement of pore water ions in opposite directions, leading to charge interactions that can affect the distribution of charged species in the domain. Here, we demonstrate that changes in chemical conditions, such as the concentration of a background electrolyte in the pore water of a saturated porous medium, exert a key control on the macroscopic transport of charged tracers and reactants. The difference in concentration between the background electrolyte and an injected solute can limit or enhance the reactant delivery, cause nonintuitive patterns of concentration distribution, and ultimately control mixing and degradation kinetics. With nonreactive and reactive electrokinetic transport experiments combined with process-based modeling, we show that microscopic charge interactions in the pore water play a crucial role on the transport of injected plumes and on the mechanisms and rate of both physical and chemical processes at larger, macroscopic scales. Our results have important implications on electrokinetic transport in porous media and may greatly impact injection and delivery strategies in a wide range of applications, including in situ remediation of soil and groundwater.